DE10111231A1 - Method and device for homogeneous mixing of a solid phase in finely divided form with a fluid - Google Patents

Abstract

The present invention provides methods for homogeneously mixing a solid phase in finely divided form with a fluid in a vessel (12), a means (11) for mixing the solid phase being movably arranged in the vessel (12) and the diameter the mean (11) is 70-99% of the inside diameter of the vessel (12). The present invention further comprises an array which comprises a multiplicity of devices according to the invention for the parallelisable homogeneous mixing of a multiplicity of solid phases with identical or different fluorides.

Description

The present invention relates to a method and an apparatus for homo gene mixing of a solid phase present in finely divided form with a fluid according to the preambles of independent claims 1 and 7, and an array, which a variety of devices according to the invention includes.

In processes for coating or for impregnating solid phases or Powders or granules of solids, especially under mechanical agi Two different techniques are generally used. To the one is powder, granules or molded articles with a so-called "rotating Addition "arrangement continuously soaked with liquids. This is at described for example in C. Perego et al. "Catalysis today" 34 (1997), pp. 281-305; ff. in "Preparation of solid Catalysts" editor G. Ertl, H. Knüzinger, J. Weitkamp, page 579, Verlag Chemie, Weilheim, 1999.

Here, a rotating plate or a rotating drum with a be agreed wall height and a certain angle to the horizontal. A powder or granulate is placed in or on this rotating drum  given rotating plate, and the rotation of the drum or the plate ensures for mixing powder or granules with the solution to be introduced solution or the liquid.

By the height of the plate edge and the angle of inclination of the plate, or the Drum can affect the residence time and thus the degree of impregnation of the molded body be set on the plate. With this arrangement, is for the impregnation process requires a certain shaped body size for successful impregnation, because below a certain size, those acting on the molded body Gravity against the adherence of the molded body on the plate or Drum due to capillary forces in the presence of distributed on the plate Liquid are too small to reach moldings below a certain size let it rotate on the plate or drum approx. less than 5 millimeters. That is, the method described above is not arbitrarily scaled down bar. Another disadvantage of this method is that it is only soaked up occurs to a certain degree of liquid absorption of the molded body, followed by a "rising" of the moldings and a The viscosity increases roughly, so that the impregnated material is thoroughly mixed, d. H. the molded body is no longer satisfactory. Typically in this Cases continued in a so-called pan mill.

So-called rumbling is the second option mentioned above de. The rumbling takes place in typical pan mill, in which powder through Rolling is kneaded and by the introduction of mechanical energy too at high levels of moisture, the powders are thoroughly mixed with egg fluid is ensured. Disadvantages of the known Koller methods are just if there is no way to miniaturize it, because pan mill a must have a certain size.  

Koller processes also allow the use of granules or larger ones Shaped bodies instead of finely divided powders, because these mechanical influence of the rollers would be destroyed.

These processes are widely used in the chemical and manufacturing sectors material sciences. This applies e.g. B. also on the production of heterogeneous Catalysts through combinatorial processes. These are especially so called supported catalysts, which are widely used because they are relative having a high content of an active component on a surface of a body a high degree of thermal stability of the catalytic component ver a.

In view of the disadvantages described above with respect to the methods of the prior art, the object was therefore to develop a method and a device for homogeneous mixing of a solid phase with a fluid that is present in a finely divided form that the aforementioned disadvantages of the prior art Avoids technology and meets the following requirements:

• 1. good mechanical mixing at both high and low Moisture content of the powder or granules.
• 2. Impregnation of moldings or granules without their mechanical destruction tion.
• 3. Possibility of miniaturizing the process

These objects are achieved by the present invention in that the method according to the invention a means for mixing the solid Pha is used in a vessel that is movable in a vessel is ordered and the diameter of this agent is 70-99% of the inside diameter of the vessel. This creates a permanent mechanical Mixing of the solid phase, which for example consists essentially of one Powder, granules or other shaped bodies can exist.

Said granules or moldings, from which the solid phase essentially can exist without mechanical destruction with a fluid for example, a liquid mixed homogeneously, d. H. be soaked.

It is preferred that the primary structure of the solid phase is essentially unchanged remains, so that easily breakable granules or moldings of the inventive method can be mixed with a fluid.

It is particularly preferred that the solid phase has a porous primary structure points, so that by adjusting the porosity a certain amount of fluid, which is preferably a liquid.

The fluid is preferably introduced homogeneously into the solid phase, so that a uniform mixing of the solid phase by the erfindungsge appropriate procedure is made possible.

In a further preferred embodiment, the method is parallelized performed so that a variety of different solid phases at the same time can be mixed homogeneously with a fluid.  

The object of the present invention is further achieved by a device for Implementation of the method according to the invention solved, the device a solid phase mixing means comprising be in a vessel is arranged movably and wherein the diameter of the means for mixing the solid phase is 70-99% of the inside diameter of the vessel. Due to the size ratio between the through determined according to the invention the device is the mean and the inner diameter of the vessel adapted to the process so that mechanical mixing of the solid Phase is allowed during the homogeneous mixing with a fluid.

It is preferred that the means for mixing the solid phase is permanent is magnetic or magnetizable and the further means for creating a magnetic field are provided, the magnetic field being continuous or can be changed periodically.

This means that the means of mixing in the vessel is easy to move guaranteed by appropriate means the speed of the means that rotated in the vessel, for example. The continuous or periodic situation of the magnetic field further enables an enhanced homogeneous mixing of the solid phase.

In a particularly preferred embodiment, the means for mixing the solid phase scoop-shaped area, so that the solid phase be can be mixed particularly intensively and homogeneously with a fluid.

The object of the present invention is further achieved by an array which comprises a plurality of devices according to the invention, so that one  any number of different solid phases or moldings the same also homogeneously mixed in time with different or the same fluid can be.

The terms used in the context of the present application are intended to at this point:

Fixed phase

In principle, this term encompasses a multitude of numbers that cannot be recorded numerically Shaped bodies that are in a solid state under normal conditions.

fluid

A medium is defined as a fluid or fluid medium if it is Flowability is proportional to the expression γE / RT, where γE is that energy that must be overcome for the medium to flow. This includes for example liquids, gases, waxes, dispersions, emulsions, brine, gels, Greases, suspensions, melts, powdery solids, etc.

moldings

In principle, this term includes all 3-dimensional facilities and Bodies with a rigid or semi-rigid surface that can be both flat NEN can also have openings, pores or bores or channels. The molded body must be suitable for taking up substances or a fluid medium.  With regard to the external shape of the shaped bodies, there are no beings restrictions as long as it is a 3-dimensional device or a 3- dimensional body. The shaped body can thus have the shape of a sphere or hollow sphere, or an ellipsoidal body, a cuboid, a cube, of a cylinder, prism or fractal body.

material

Under "material" are preferably non-gaseous substances such. B. Solids, brine, gels, waxy substances or mixtures of substances, disper sions, emulsions, suspensions or solids understood.

These can be molecular or non-molecular chemical compounds genes, formulations, mixtures act, the term "non-molecular" Defines substances that can be continuously optimized or changed, in contrast to "molecular" substances, the structural expression of which only via a variation of discrete states, e.g. the Variation of a substitution pattern can be changed.

monomodally

In the present application, “monomodal” means that the Shaped bodies consist only of a geometric shape that is essentially ho mogen, with their particle size distribution (TGV) ± 30% of the median of the general particle size distribution.  

As a conceptual contrast to this, the term "polymodal" is because the molded articles can consist of any number of geometric shapes, thus the moldings are essentially not homogeneous.

porosity

Bodies have a porosity, ie they are porous if they have micropores, me sopores and / or macropores according to the IUPAC definition or a combination of two or more thereof, it being possible for the pore distribution to be mono-, bi- or multimodal. In the context of the present invention, the bodies preferably have a multimodal pore distribution with a high, ie with more than 50%, proportion of macropores. Examples of these are foam ceramics, metallic foams, metallic or ceramic monoliths, hydrogels, polymers, in particular PU foams, composites, sintered glasses or sintered ceramics. The porosity of such a shaped body generally has a BET surface area of 1 to 1000, preferably 2 to 800 and in particular 3 to 100 m ² / g.

primary structure

The term "primary structure" is intended to mean the state of the constituents of the solid phase describe before it is subjected to a mixing process. such Conditions can be, for example: a special porosity, no porosity, a defined surface quality, a defined morphology, in particular their size, shape and shape of the particles.

Further advantages and configurations of the inventions result from the Be description, the embodiment and the accompanying drawings.  

It is understood that the above and those mentioned below Features still to be explained not only in the combination specified on, but can also be used in other combinations or alone, without departing from the scope of the present invention.

The invention is based on an embodiment and in the drawings is shown schematically and is described below with reference to the drawing described in detail.

Fig. 1 shows schematically an inventive device according to claim 7.

Fig. 2 shows schematically a further embodiment of the device according to claim 7.

FIG. 3 shows in FIGS . 3a and 3b two different embodiments of a means for mixing a solid phase with a fluid.

Fig. 1 shows schematically an embodiment of the device according to the invention according to claim 7. The device ( 10 ) comprises a vessel ( 12 ), the bottom of which is rounded. The vessel ( 12 ) is filled to a previously defined height H with a solid phase, for example a finely divided powder ( 13 ). In the solid phase ( 13 ) there is a means ( 11 ) for mixing the solid phase. The means ( 11 ) is designed in the present case in the form of a disc-shaped structure standing on the edge. The diameter d of the disc-shaped means ( 11 ) is 75% of the inside diameter D of the vessel ( 12 ). In this embodiment according to FIG. 1, a vessel ( 12 ) with a rounded bottom is particularly preferred because of the shape of the agent ( 11 ), since the portions of the solid phase located under the agent ( 11 ) are thus mixed particularly homogeneously can.

The size and weight of the agent ( 11 ) are of course adjusted accordingly to the respective composition or the physical character of the solid phase ( 12 ).

The appropriate dimensioning of the means ( 11 ) for mixing thus allows the use of a large number of solid phases, that is to say, for example, of powders of different densities and constitution, which have to be mixed homogeneously with a fluid. Furthermore, the targeted dimensioning of the agent ( 11 ) also allows a targeted selection from a large number of different fluids.

Fig. 2 is a further schematic illustration showing an embodiment of the inventive device.

The device 20 comprises a vessel ( 22 ) in which a solid phase, for example a finely divided granulate or a finely divided powder, is introduced up to a height H. The vessel ( 22 ) has a flat bottom in this case. In the solid phase 23 there is a means ( 21 ) for mixing the solid phase. The ratio of the diameter d of the means ( 21 ) for mixing the solid phase ( 23 ) is 75% of the inner diameter D of the vessel ( 22 ).

As already explained above under Fig. 1, suitable dimensioning of the two diameters d and D can react appropriately to different material requirements with regard to the solid phase and the fluid.

Both in Fig. 1 and in Fig. 2 devices are not shown before, for example magnetic stirrers or the like, which a periodic or continuous rotation of the means ( 11 ) or ( 21 ) for mixing in the fixed phase ( 13 ) or . ( 23 ) enable. Both in Fig. 1 and in Fig. 2 be means ( 11 ) or ( 21 ) from a Teflon coated magnetisierba ren iron core.

Fig. 3 shows in Fig. 3a an embodiment of a means ( 11 ) for mixing the solid phase (here referred to as means ( 30 )). The means ( 30 ) comprises cross-shaped, bar-shaped iron cores coated with Teflon. A bar-shaped part ( 31 ) is on the other bar-shaped part ( 32 ) in firm and direct contact. The dimension of the means ( 30 ) also depends on the dimensioning of the corresponding vessel in which the component ( 30 ) is subsequently used to mix a solid phase.

FIG. 3b shows a further embodiment of the means (11) (referred to herein as means (40)) for mixing a solid phase. In this case, the means ( 40 ) consists of a disc-shaped body which can, for example, rotate upright, as is shown, for example, in FIG. 1. On the diskusför shaped body ( 41 ) two scoop-shaped components ( 42 ) and ( 43 ) are arranged in a fixed connection analogous to Fig. 3a. The blade-shaped elements ( 42 ) and ( 43 ) achieve particularly good mixing of a solid phase in a corresponding vessel, which preferably has a rounded bottom. The scoop-shaped elements ( 42 ) and ( 43 ) can be arranged only on one side of this disc-shaped molding ( 41 ), but also on both sides of the disc-shaped molding ( 41 ). This can be varied depending on the solid phases used.

The process according to the invention can be used in a simple manner heterogeneous or heterogenized catalysts, luminophores, thermoelectric, piezoelect nical, semiconducting, electro-optical, superconducting or magnetic substances or mixtures of two or more of these substances, especially intermetalli cal compounds, oxides, oxide mixtures, mixed oxides, ionic or kova lent connections of metals and / or non-metals, metal alloys, Kermaiken, organometallic compounds and composite materials, The electronics, thermoelectrics, magnetoresistive and magneto-optical materials, organic compounds, enzymes and enzyme mixtures, pharmaceutical Active substances, substances for feed and feed supplements, substances for food and food supplements and cosmetics and gemi cal of two or more oxides are used as the solid phase.

The inside of this disc-shaped body ( 41 ) comprises a core made of iron or other permanent magnetic or permanently magnetizable alloys or metals or, for example, a puck-containing alloy. The invention is explained below using an example.

example

1 g of silicon dioxide (Sipernat D22, from Degussa) is in each case in a reak tion vessel submitted (inner diameter of the reaction vessel made of glass is 20 mm, the reaction vessel has a round bottom). The reaction vessel was with provided a magnetic fish. The magnetic fish was a round disk with one Diameter of 16 mm and a width of 8 mm. On a magnetic stirrer the sample is heated from room temperature to 80 ° C in 30 minutes and at 2000 Revolutions per minute. At higher revs open the disc and fluidize the powder.  

Various amounts of iron nitrate (concentrations: c = 1 mol / L) were metered in with a pipetting robot:

The delivery rate was 50 µl / sec. Samples 3 and 4 were after 1250 µl the metering is interrupted for 10 minutes so that the Liquid can evaporate. Then the remaining 1250 µl are added Siert. The samples are stirred for 30 minutes.

The samples were dried in a circulating air drying cabinet at 60 ° C. for 15 hours net. The dried powder was transferred to porcelain bowls and inside brought from 60 minutes to 600 ° C and held at 600 ° C for 1 hour.

In the calcined samples, the fine fraction of <30 µm was sieved and ver worfen.  

Using a Micromeritrics TriStar nitrogen absorption device, the surfaces of the samples are determined using a 3-point BET measurement. For heating, the samples were previously brought to 400 ° C. at 20 ° C. per minute and kept at 400 ° C. for 3 hours.

The grain size distribution was determined using an Olympus AX70 microscope. 3 images per sample were taken and evaluated. A total of approx. 150 particles per sample were measured. Only particles with an area larger than 100 µm ^{2 were used} for the determination.

For easier illustration, the grain size distribution was divided into classes Splits. The particle frequency shown as a histogram gave the following picture:  

Sample 1

Sample 2

Sample 3

Sample 4

SiO ₂ , Sipernat D22

Claims (15)

1. A method for homogeneous mixing of a solid phase in a finely divided form with a fluid in a vessel ( 12 ), wherein a means ( 11 ) for mixing the solid phase in the vessel ( 12 ) is movably arranged and wherein the diameter the mean ( 11 ) is 70-99% of the inside diameter of the vessel ( 12 ). 2. The method according to claim 1, characterized in that the primary structure the solid phase remains essentially unchanged. 3. The method according to claim 1 or 2, characterized in that the fixed Phase is a powder or granules. 4. The method according to claim 3, characterized in that the fluid in the solid phase is entered homogeneously, inhomogeneously or combinatorially. 5. The method according to any one of the preceding claims, characterized net that the fluid comprises one or more components. 6. The method according to any one of the preceding claims, characterized in net that the process automates in parallel or automates sequentially is carried out.   7. A device ( 10 ) for homogeneously mixing a solid phase in finely divided form with a fluid, comprising a vessel ( 12 ) and a means ( 11 ) for mixing the solid phase ( 13 ) which is movable in the vessel ( 12 ) is arranged and wherein the diameter of the means ( 11 ) is 70-99% of the inner diameter of the vessel ( 12 ). 8. The device according to claim 7, characterized in that the means ( 11 ) is permanently magnetic or permanently magnetizable. 9. The device according to claim 8, characterized in that a means for A magnetic field is provided. 10. The device according to claim 9, characterized in that the magnetic Field can be changed locally or periodically. 11. Device according to one of the preceding claims, characterized in that the means ( 11 ) has blade-shaped areas. 12. Array comprising a plurality of devices according to one of the claims 7-11. 13. Computer program with program code means for carrying out the Ver driving according to one of claims 1 to 6. 14. Data carrier with computer program according to claim 13. 15. Computer program according to claim 13 for implementation with the help of the front Direction according to one of claims 7 to 11.